Anti-vesicant composition



2,921,031 ANTI-VESICANT COMPOSITION Harry Scherr, Baltimore, Md.,assignor to the United States of America as represented by the Secretaryof War as trustee v i No Drawing. Application May 30, 1942 Serial No.445,221

6 Claims. (Cl. 252-187) (Granted under Title 35, U.S. Code (1952), sec.266) The invention described herein may be manufactured and used by orfor the Government for governmental purposes without the payment to meof royalty thereon.

This invention relates generally to protective clothing adapted toafford personnel protection against known chemical warfare vesicantagents such as mustard gas and lewisite, and the invention relates inparticular to compositions to be used in providing such protectiveclothing.

It has been found that known chemical warfare vesicant agents, such asmustard gas and lewisite, may be rendered non-vesicant and relativelyharmless by some type of halogenation, and particularly by chlorination,so as to convert the vesicants into innocuous products. Conceivably,-anycompound having an available halogen atom may be considered as havingpossible use as an anti-vesicant agent for halogenating or 'chlorinatingvesicants. However, due to practical considerations, the chloramideshave been found to be most suitable, as a class, to be used aschlorinating agents. Of the class of chloramides, bis dichlorphenylchlorurea and bis 2,4,6- trichlorphenyl chlorurea have been found to bevery satisfactory anti-vesicant agents.

Considerable difliculty has been encountered in, the past in developingcompositions and techniques whereby fabric and clothing may be treatedwith the anti-vesicant agents so as to leave sufficient deposits thereofin the fibers of the fabric or clothing to give effective protectionagainst vesicants and which will adherefirmly thereto so as to resist areasonable amount of wearand laundering. Generally, the anti-vesicantagents and suitable. inert binders have been dissolved in variousvolatile organic solvents so as to provide a so-called impregnatingcom-. position. The fabric and clothing have then been soaked solutionsto provide increased solubility of the antirelatively low concentrationsof anti-vesicant agents in the impregnating compositions, a large amountof solvent evaporation was required for the amount of anti-vesicantagent deposited in the fabric or clothing.

In view of the foregoing difiiculties of the prior art, one of theprincipal objects of the present invention is the provision ofimpregnating compositions for treating fabric or clothing to render thesame resistant to chemical warfare vesicants, such as mustard gas andlewisite, which compositions contain in uniform distribution, and atordinary temperatures, amounts of anti-vesicant or neutralizing agentsin excess of the amounts normally soluble therein. Such improved andrelatively concentrated impregnating compositions permit verysatisfactory impregnation of fabric and clothing at ordinarytemperatures, and eliminate the most objectionable difficulties of theprior art in regard to the heating of the impregnating compositions andthe extended drying periods required to remove the volatile solvents.

A further object of this invention is the provision of impregnatingcompositions containing dyeing or coloring material whereby fabric andclothing may, in one operation, be simultaneously dyed and renderedresistant to chemical warfare vesicants such as mustard gas and obviousresides in the inclusion in an impregnating composition; of aningredient which serves to maintain a substantially uniform distributionthroughout the composition of an amount of an anti-vesicant agent inexcess of that amount thereof which would be normally soluble and remainuniformly distributed. .When the impregnating composition has only oneliquid phase, the added ingredient serves as a suspending agent, whilein certain instances where an impregnating composition is in the form ofan' emulsion having two liquid phases, the added ingredient appears tofunction as an emulsifying agent.

For a more complete understanding of the nature and scope of thisinvention, reference may be had to the following detailed descriptionmentioning certain specific compositions and techniques as illustrative.

One type of impregnating compositions embodying the invention has asingle liquid phase and comprises, in

general, an anti-vesicant agent having available chlorine for destroyingmustard gas, lewisite and like vesicants, and a hinder, the antivesicantagent and binder being dissolved in an organic solvent in which asuspending agent has been dissolved. The anti-vesicant agents may besuch compounds as his dichlorphenyl chlorurea or bis2,4,6-trichlorphenyl chlorurea, both compounds being selected from thegeneral class of chloramides. Several binders may be used which areinert to the anti-vesicant' agents, such as chlorinated napthalene(Halowax) and chlorinated parafiln. Various organic solvents may be usedsuch as monochlorbenzene, beta trichlorethane, and perchlorethylene.These solvents may be classed as chlororganic solvents. As an example ofa suspending agent, ethyl cellulose has been found to be verysatisfactory for the purposes intended.

Irnpregnating compositions may include the foregoing 7 ingredients orcomponents in various percentage ranges. a By way of example, verysatisfactory impregnating com- Patented Jan. 12, 19.60

positions may bemade according to the following formula:

Percent by weight Ethyl cellulose -4 0.30.5

Monochlorbenzene 5 00-600 Beta trichlorethane 30.0-34.0 Chlorinatednaphthalene 1.5-2.5 Chlorinated paraffin 3.0-4.0- Bis2,4,6-trichlorphenyl chlorurea 5.0-8.0

An impregnating composition having the above general formula may beprepared according to the following steps:

(3) Finally, and preferably just prior to the use of the impregnatingcomposition, the bis 2,4,6-trichlorphenyl chlorurea is added. 1 V

(4) On shaking or other mild agitation, a stable suspensionof lowviscosity results. All steps are carried out at ordinary temperatures; a

The technique of impregnating clothing with the forei going type ofimpregnating compositions is simple and may be referred to as thesuspension process. Clothing, without previous drying, is immersed inthe impregnating composition and soaked for a few minutes so as tothoroughly wet the same. The clothing is then removed and wrung out soasto remove the'impregnating composition in excess of that required foradequate im-' pregnation. It will be n oted that the impregnation iscarried out at ordinary temperatures without treating,

and is adapted to either large, or small scale field impregnation.

According to one embodiment of the invention, irhpregnating compositionsmay be prepared which may beused to simultaneously dye and impregnatefabric and clothing in one stage at ordinary temperatures. Severalclasses of dyestuflis may be used, such as: solvent solubleanthraquinone dyestuifs; water soluble anthraquinone' dye-' stuffs;pigment powders; pigment pastes; and, flushed pigments- The flushedpigments have been found to be very suitable for the purpose intended;Thesepigm'ents are produced by first grinding the pigment in water andthen transferring or flushing the pigment particles to a medium such asone consisting of ethyl cellulose and monochlorbenzene. The resultingflushed pigment corn- Chlorinated parafiin position maythen bereadily'incorporated in the base solution used in'the suspension processfor clothing im- 7 pregnation.

'While the present invention was particularly concerned with imparting akhaki shade to white cotton drill, it will be understood that anydesired color may beimparted to clothing or. fabric by the properselection of the pigments in the flushed pigment mixture. A typicalformula for an impregnating composition adapted to provide for thesimultaneous dyeing and impregnation of white cotton drill to give akhaki shade to the clothing is as follows:

An impregnated and dyeing composition following the above generalformula, may be prepared according to the following steps:

(1) The ethyl cellulose is dissolved in the monochlorv benzene and betaI trichloroethane, giving aclear, colorless solution.

(2) The chlorinated naphthalene and chlorinated paraffin are added tothe solution of step 1.

(3) The flushed pigment is thoroughly mixed into the solution from step2. N

(4) Finally, and preferably just prior to the use of the composition,the his 2,4,6-trichlorphenyl chlorurea is added with shaking or othermild agitation.

The technique of treating fabric or clothing with a combinedimpregnating and dyeing composition is the same as that describedhereinbefore in connection with the compositions used only forimpregnation.

According to a further embodiment of the invention, emulsion-typeimpregnating compositions have been prepared which can be used forimpregnating clothing or. fabric with anti-vesicant material. Theseemulsions require strong mechanical agitation such as obtained by acolloid mill or homogenizer. Several types of emulsifying agents may beused to impart reasonable stability to the emulsions. The following is alist of some of the emulsifying'agents that may be used:

Monochlorbenzene -l -;l.. l; 15"

Perchlorethylene 10 5' Emulsifying agent 3' Bis 2,4,6-trichlorphenyl:chlorurea 7 Water; 60

The emulsion is prepared byfirst making a mixture of themonochlorbenzene, .p'erchlore'thylene, chlorinated paraffin, emulsifyingagent, 'and bis2,4,6-trichlorphenyl chlorurea. The proper amount ofwater'is then added to V the above mixture, and the complete mixture isthen passedthru a colloid mill to give a homogeneous,'stablc emulsion. vI

Clothing and fabric may be impregnated .in the emul- 81011831. ordinarytemperatures in the usual manner. Since certain changes andmodifications may be made 1n the. foregoing compositionsand techniques.of applicatron without departing from the scope of this invention, itis intended that all matter contained in the abovedcscrlption shall beinterpreted as illustrative and not in a limited sense.

What is-claimed as newis: V -1. A fabric impregnating composition forrendering fabric and clothing resistantto mustard gas, lewisite, andlike: vesicants susceptible of being rendered non-vesicant bychlorination, which'compn'ses, bis 2,4,6-trichlorphenyl chlorurea' forrendering mustard gas, lewisite, and like vesicants relatively harmless,a binder'comprising a mixture of chlorinated paraffin and chlorinatednaphthalene, a solvent comprising a mixture of monochlorbenzene' andbeta trichl'orethane, and a small amount of ethyl cellulose as asuspending agent for maintaining a relatively stable suspension'of bis2,4,6-trichlorphenyl chlorurea in the solvent. V V

2. A fabric impregnating composition for rendering fabric and clothingresistant to mustard gas, lewisite', and

like vesicants susceptible of being'rendered non-vesicant' bychlorination, which c0mprises,.from about5'.0% .to

8.0% r by weight of bis"2,4,6-trichlorphenyl2 chlorure'a for renderingmustard gas, lewisite, and like vesicants relacomposition may havethefol- V about 1.5% to 2.5% by weight of chlorinated naphthalene and fromabout 3.0% to 4.0% by weight of chlorinated parafiin, a solventcomprising a mixture of from about 50.0% to 60.0% by weight ofmonochlorbenzene and from about 30.0% to 34.0% by weight ofbeta-trichlorethane, and about 0.3% by weight or greater of ethylcellulose as a suspending agent for maintaining a relatively stablesuspension of his 2,4,6-trichlorphenyl chlorurea in the solvent.

3. A fabric impregnating composition for simultaneously coloring andrendering fabric and clothing resistant to mustard gas, lewisite, andlike vesicants susceptible of being rendered non-vesicant bychlorination, which comprises, bis 2,4,6-trichlorphenyl chlorurea forrendering mustard gas, lewisite, and like vesicants relatively harmless,a binder comprising a mixture of chlorinated parafiin and chlorinatednaphthalene, flushed pigment for coloring said fabric or clothing, asolvent comprising a mixture of monochlorbenzene andbeta-trichlorethane, and a small amount of ethyl cellulose as asuspending agent for maintaining a relatively stable suspension of bis2,4,6-trichlorphenyl chlorurea in the solvent.

4. A fabric impregnating composition for simultaneously coloring andrendering fabric and clothing resistant to mustard gas, lewisite, andlike vesicants susceptible of being rendered non-vesicant bychlorination, which comprises, from about 4.7% to 7.5% by weight of bis2,4,6-trichlorphenyl chlorurea for rendering mustard gas, lewisite, andlike vesicants relatively harmless, a binder comprising a mixture offrom about 1.4% to 2.4% by weight of chlorinated naphthalene and fromabout 2.8% to 3.8% by weight of chlorinated paraffin, about 6% by weightof a flushed pigment for coloring said fabric or clothing, a solventcomprising a mixture of from about 47.0% to 56.4% of monochlorbenzeneand from about 28.2% to 32.0% by weight of beta-trichlorethane, andabout 0.28% by weight or greater of ethyl cellulose as a suspendingagent for maintaining a relatively stable suspension of his2,4,6-trichlorphenyl chlorurea in the said solvent.

5. A fabric impregnating composition for rendering fabric and clothingresistant to mustard gas, lewisite, and like vesicants susceptible ofbeing rendered non-vesicant by chlorination, and which is in the form ofan oil-inwater emulsion having an oil phase comprising bis 2,4,6-

like vesicants susceptible of being rendered non-vesicant bychlorination, and which is in the form of an oil-in- Water emulsionhaving an oil phase comprising about 7% by weight of the composition ofhis 2,4,6-tn'chlorphenyl chlorurea for rendering mustard gas, lewisite,and like vesicants relatively harmless, a binder comprising about 5% byweight of the composition of chlorinated parafiin, and a solventcomprising a mixture of about 15% by weight of the composition ofmonochlorbenzene and about 10% by weight of the composition ofperchlorethylene, having a water phase comprising about by weight of thecomposition, and having an emulsifying agent to stabilize the emulsioncomprising about 3% by weight of the composition.

References Cited in the file of this patent UNITED STATES PATENTS1,085,783 Aylsworth Feb. 3, 1914 1,907,521 Dreyfus May 9, 1933 1,950,957Wilhelm Mar. 13, 1934 1,958,370 Schmelkes July 8, 1934 2,073,256Schmelkes Mar. 9, 1937 2,136,173 Steingroever Nov. 8, 1938 2,275,593Muskat Mar. 10, 1942 2,299,612 Clayton Oct. 20, 1942 FOREIGN PATENTS588,131 Germany July 3, 1929 590,818 Germany Jan. 11, 1934 486,162 GreatBritain May 31, 1938 496,734 Great Britain Dec. 5, 1938 OTHER REFERENCESHoogeveen: Gas Clothing, Chemisch Weekblad (1936), vol. 33, pages 474,475, in Dutch, translation in Div. 3.

1. A FABRIC IMPREGNATING COMPOSITION FOR RENDERING FABRIC AND CLOTHINGRESISTANT TO MUSTARD GAS, LEWISITE, AND LIKE VESICANTS SUSCEPTIBLE OFBEING RENDERED NON-VESICANT BY CHLORINATION, WHICH COMPRISES, BIS2,4,6-TRICHLORPHENYL CHLORUEA FOR RENDERING MUSTARD GAS, LEWISTE, ANDLIKE VESICANTS RELATIVELY HARMLESS, A BINDER COMPRISING A MIXTURE OFCHLORINATED PARAFFIN AND CHLORINATED NAPHTALENE, A SOLVENT COMPRISING AMIXTURE OF MONOCHLORBENZENE AND BETA-TRICHLORETHANE, AND A SMALL AMOUNTOF ETHYL CELLOUSE AS A SUSPENDING AGENT FOR MAINTAINING A RELATIVELYSTABLE SUSPENSION OF BIS 2,4,6-TRICHLORPHENYL CHLORUREA IN THE SOLVENT.